US4020042A - Phenolic antioxidants - Google Patents
Phenolic antioxidants Download PDFInfo
- Publication number
- US4020042A US4020042A US05/525,439 US52543974A US4020042A US 4020042 A US4020042 A US 4020042A US 52543974 A US52543974 A US 52543974A US 4020042 A US4020042 A US 4020042A
- Authority
- US
- United States
- Prior art keywords
- butyl
- carbon atoms
- mercaptopropionate
- group
- hydroxyphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002530 phenolic antioxidant Substances 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- -1 alkyl radicals Chemical class 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- XNAQFHAPGGRYKF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl 2-sulfanylacetate Chemical compound CC(C)(C)C1=CC(COC(=O)CS)=CC(C(C)(C)C)=C1O XNAQFHAPGGRYKF-UHFFFAOYSA-N 0.000 claims 1
- JOIOORPEYSFHJK-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl 2-sulfanylpropanoate Chemical compound CC(S)C(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JOIOORPEYSFHJK-UHFFFAOYSA-N 0.000 claims 1
- XOXZKRLTVGADPR-UHFFFAOYSA-N 4-(3,5-ditert-butyl-4-hydroxyphenyl)butan-2-yl 3-sulfanylpropanoate Chemical compound SCCC(=O)OC(C)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XOXZKRLTVGADPR-UHFFFAOYSA-N 0.000 claims 1
- WCALWFBKOIGUTM-UHFFFAOYSA-N [3-(3,5-ditert-butyl-4-hydroxyphenyl)-2,2-dimethylpropyl] 3-sulfanylpropanoate Chemical compound CC(C)(C)C1=CC(CC(C)(C)COC(=O)CCS)=CC(C(C)(C)C)=C1O WCALWFBKOIGUTM-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 238000012667 polymer degradation Methods 0.000 abstract 1
- 238000010186 staining Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229940044613 1-propanol Drugs 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- OAHOSAFPDBZWAU-UHFFFAOYSA-N (3-cyclooctyl-4-hydroxy-5-methylphenyl)methyl 3-sulfanylpropanoate Chemical compound CC1=CC(COC(=O)CCS)=CC(C2CCCCCCC2)=C1O OAHOSAFPDBZWAU-UHFFFAOYSA-N 0.000 description 1
- WUJZYADXVBMLJQ-UHFFFAOYSA-N (3-cyclopentyl-4-hydroxyphenyl)methyl 2-sulfanylacetate Chemical compound OC1=CC=C(COC(=O)CS)C=C1C1CCCC1 WUJZYADXVBMLJQ-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- HJBNPHZFWDSJLR-UHFFFAOYSA-N 2,6-dicyclopentyl-4-(2-hydroxyethyl)phenol Chemical compound OC=1C(C2CCCC2)=CC(CCO)=CC=1C1CCCC1 HJBNPHZFWDSJLR-UHFFFAOYSA-N 0.000 description 1
- LLZSGWFRZMQVBG-UHFFFAOYSA-N 2-decyl-4-(3-hydroxybutan-2-yl)phenol Chemical compound CCCCCCCCCCC1=CC(C(C)C(C)O)=CC=C1O LLZSGWFRZMQVBG-UHFFFAOYSA-N 0.000 description 1
- ZVXBWEIAIZEPGR-UHFFFAOYSA-N 4-(hydroxymethyl)-2,6-dimethylphenol Chemical compound CC1=CC(CO)=CC(C)=C1O ZVXBWEIAIZEPGR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Definitions
- This invention relates to a composition of matter having an improved stabilizing effect on oxidizable organic materials. More particularly this invention relates to new phenolic antioxidants and to polymer compositions containing these materials and to a method of preparing these materials by reacting a phenolic compound with compounds capable of producing a phenolic ester thiol.
- the compounds described above can be prepared by reacting phenolic compounds containing reactive hydroxyl groups having a general structural formula selected from the group consisting of ##STR2## with ester forming compounds having the general formula ##STR3## wherein R 1 , R 2 , B, Y, m and A are the same as described above and E is selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 3 carbon atoms.
- the reaction can be catalyzed by small amounts of acidic catalyst, although catalysts may not be necessary in some reactions.
- the amount of catalyst used can vary widely. However from 0.25 gram to 5.0 grams of catalyst per 100 grams of reactants is usually sufficient. Higher levels of catalyst can be used but usually yield no advantage.
- Representative examples of acidic catalysts useful in the present invention are toluenesulfonic acid, sulfuric acid, boron trifloride, benzenesulfonic acid, hydrochloric acid, phosphoric acid, ion exchange resins and acid-activated clays.
- the reaction may be run without solvent. However solvents such as xylene, benzene or toluene usually aid in carrying out the reaction.
- the reaction can be run at room temperature, but usually is run at a temperature up to the boiling point of the solvent. If no solvent is used the reaction is carried out below the boiling point of the reactants.
- the molar ratio of phenolic to ester forming compound is 1:1, however excess ester forming compound may be used to speed up the reaction and reduce side reactions. Any amount of excess ester forming compound can be used; however molar ratios of phenolic to ester forming compound of from 1:1 to 1:2 are preferred.
- phenolic starting materials useful in this invention are:
- ester forming compounds are:
- the compounds of this invention are useful in clear polymers such as polypropylene and polyethylene because of their clarity. These compounds also are superior to those known in the prior art for preventing the hardening of oxidizable polymers. These compounds in addition may function as chain transfer agents.
- the free thiol (-SH) group allows these compounds to be chemically incorporated to some extent, into polymers during processing. The compound can prevent hardening in styrene-butadiene polymers.
- the stabilizers of this invention are employed from about 0.0005 percent to about 10 percent by weight of the stabilized composition, although this will vary with the particular polymer. A particularly advantageous range is from about 0.025 percent range to about 1.5 percent.
- the compounds are especially useful for the stabilization of polyethylene and polypropylene but are also effective in olefin polymers.
- a compound of this invention was also tested for color characteristics in polypropylene and compared to a clear polypropylene containing no antioxidant.
- Profax 6501 is clear polypropylene containing no stabilizer and sold by Hercules Chemical Company.
- Rd is a measure of reflectance on the Gardner Colorimeter based upon a MgO standard given the value of 91.1. This value indicates position along a neutral color axis from black to white with high values indicating high reflectance or brightness.
- the symbol "a” is an expression of the dominant colors of red (if a positive value) and of green (if a negative value). Intensity of either color is indicated by the magnitude of the value regardless of sign.
- the standard is magnesium oxide given the value of 0.0.
- the symbol "b” is an expression of the dominant colors of yellow (if a positive value) and of blue (if a negative value). Intensity of either color is indicated by the magnitude of the value regardless of sign.
- the standard is magnesium oxide given the value of 0.0.
- the color index is a measure of the total polymer color characteristics and is calculated by ##EQU1##
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/525,439 US4020042A (en) | 1974-11-20 | 1974-11-20 | Phenolic antioxidants |
| BE174297A BE850648A (fr) | 1974-11-20 | 1977-01-21 | Antioxydants phenoliques pour polymeres et leur procede de preparation |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/525,439 US4020042A (en) | 1974-11-20 | 1974-11-20 | Phenolic antioxidants |
| BE174297A BE850648A (fr) | 1974-11-20 | 1977-01-21 | Antioxydants phenoliques pour polymeres et leur procede de preparation |
| BE850648 | 1977-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4020042A true US4020042A (en) | 1977-04-26 |
Family
ID=27158620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/525,439 Expired - Lifetime US4020042A (en) | 1974-11-20 | 1974-11-20 | Phenolic antioxidants |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4020042A (fr) |
| BE (1) | BE850648A (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239803A (en) * | 1976-06-17 | 1980-12-16 | Argus Chemical Corporation | Ethylene polymer composition |
| US4439615A (en) * | 1980-03-03 | 1984-03-27 | Ciba-Geigy Corporation | Mercaptophenol stabilizers |
| US4532286A (en) * | 1979-03-09 | 1985-07-30 | Ciba-Geigy Corporation | Stabilized rubber or lubricant compositions containing mercaptoalkyl esters of hindered phenols |
| US4820756A (en) * | 1986-06-26 | 1989-04-11 | Ciba-Geigy Corporation | Thioether substituted phenols and their use as stabilizers |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951052A (en) * | 1958-03-31 | 1960-08-30 | Monsanto Chemicals | Light stabilizer mixture |
| US3144422A (en) * | 1962-01-03 | 1964-08-11 | Carlisle Chemical Works | Polyolefins stabilized with pentaerythritol mercapto esters |
| US3496211A (en) * | 1966-05-19 | 1970-02-17 | Geigy Chem Corp | Preparation of cyanoalkylated phenols by the reaction of a metal cyanide and hydroxy benzyl phenols |
| US3536661A (en) * | 1967-07-03 | 1970-10-27 | Eastman Kodak Co | Stabilization of polyolefins and novel stabilizer compounds |
| US3637809A (en) * | 1968-07-05 | 1972-01-25 | Ciba Geigy Corp | Antioxidants |
| US3644485A (en) * | 1969-04-14 | 1972-02-22 | Eastman Kodak Co | 2-hydroxy-4-(2 - hydroxyethoxy) benzophenone esters and their use as stabilizers |
| US3676471A (en) * | 1967-12-21 | 1972-07-11 | Advance Prod Gmbh | 4-(betahydroxyethoxy-2-hydroxy-benzophenones) and esters thereof |
| US3795700A (en) * | 1971-03-10 | 1974-03-05 | American Cyanamid Co | Esters of 4-alkyl-2,6-dimethyl-3-hydroxybenzyl alcohol |
| US3829481A (en) * | 1969-03-12 | 1974-08-13 | Ici America Inc | Process for preparing a thiodiacyl halide |
-
1974
- 1974-11-20 US US05/525,439 patent/US4020042A/en not_active Expired - Lifetime
-
1977
- 1977-01-21 BE BE174297A patent/BE850648A/fr not_active IP Right Cessation
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951052A (en) * | 1958-03-31 | 1960-08-30 | Monsanto Chemicals | Light stabilizer mixture |
| US3144422A (en) * | 1962-01-03 | 1964-08-11 | Carlisle Chemical Works | Polyolefins stabilized with pentaerythritol mercapto esters |
| US3496211A (en) * | 1966-05-19 | 1970-02-17 | Geigy Chem Corp | Preparation of cyanoalkylated phenols by the reaction of a metal cyanide and hydroxy benzyl phenols |
| US3536661A (en) * | 1967-07-03 | 1970-10-27 | Eastman Kodak Co | Stabilization of polyolefins and novel stabilizer compounds |
| US3676471A (en) * | 1967-12-21 | 1972-07-11 | Advance Prod Gmbh | 4-(betahydroxyethoxy-2-hydroxy-benzophenones) and esters thereof |
| US3637809A (en) * | 1968-07-05 | 1972-01-25 | Ciba Geigy Corp | Antioxidants |
| US3829481A (en) * | 1969-03-12 | 1974-08-13 | Ici America Inc | Process for preparing a thiodiacyl halide |
| US3644485A (en) * | 1969-04-14 | 1972-02-22 | Eastman Kodak Co | 2-hydroxy-4-(2 - hydroxyethoxy) benzophenone esters and their use as stabilizers |
| US3795700A (en) * | 1971-03-10 | 1974-03-05 | American Cyanamid Co | Esters of 4-alkyl-2,6-dimethyl-3-hydroxybenzyl alcohol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239803A (en) * | 1976-06-17 | 1980-12-16 | Argus Chemical Corporation | Ethylene polymer composition |
| US4532286A (en) * | 1979-03-09 | 1985-07-30 | Ciba-Geigy Corporation | Stabilized rubber or lubricant compositions containing mercaptoalkyl esters of hindered phenols |
| US4439615A (en) * | 1980-03-03 | 1984-03-27 | Ciba-Geigy Corporation | Mercaptophenol stabilizers |
| US4820756A (en) * | 1986-06-26 | 1989-04-11 | Ciba-Geigy Corporation | Thioether substituted phenols and their use as stabilizers |
Also Published As
| Publication number | Publication date |
|---|---|
| BE850648A (fr) | 1977-05-16 |
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